Azo dyestuff components and process of preparing them



Patented Sept. 8, 1'931 UNITED STATES PATENT; OFFICE.

EDUABD SPRDNGERTS, M AXIMILIAN PAUL SCHMIDT, AND RDBERT .FRANKE, I'

WIESBAD EN-BIEBRICH, GERMANY, ASSIGNORS T0 KALLE & CO. SCHAIT, OF WIESBADEN-IBIEBRICH, GERMANY AKTIENGESELL- DYESTUFF COMPONENTS AND PROCESS OF PREPARING THEM v No Drawing. Application filed October 14, 1929, Serial No. 399,714, and in Germany October 19, 1928.

The present invention relates to azo dyestuff components and to a process of prepar- 1ng them. i

-We have found that valuable azo dye- 5 stuff components are obtained by causing a cyainamide to act upon a compound of the fol owing constitution:

,R OH wherein R stands for a naphthalene nucleus which is not substituted in ortho-. or paraposition to the hydroxy group. Thereaction is advantageously carried out in such a manner that, for instance, cyanamide or dicyana.- mide is caused to act upon the hydrochlorides of the hydroxynaphthylamines in an aqueous solution or an alcoholic'solution. The amino hydroxy compounds which are used may contain any substituents, such as, for instance, halogens, sulfo acids and others. The hydroxy aryl guanidines may contain also in the nucleus further groups, such as, for instance, sulfa1nide-, methyl-, methoxylgroups, halogen and others and in the guanidine group substituents, such as, for instance, alkylor aralkyl-groups. Finally the hydroxy group may also be substituted by such groups as are capable of being easily split off by alkali, such as, for instance, acyl groups.

The new products which are very useful --as azo dyestuffcomponents, have the following general formula:

wherein R stands for a naphthalene nucleus which is not substituted in orthoor para position to the hydroxy group and X for NH NH I IH v ride of 1.7 -amino-naphthol and parts of oyanamide are. boiled about 8 hours in an alcoholic solution. After the alcohol is.

evaporated, the residue is dissolved in hot Water, the solution is treated with animalcharcoal and filtered. Aftersoine time has elapsed, the hydrochloride of the 7-hydroxynaphthalene-l-guanidine of probably the following formula:

NHONH:.HO1

I H on crystallizes out in small, well defined crystals; by salting out, further quantities can be obtained. It is readily soluble in water, alcohol and acetone and melts at 113 C. to 114 C. The free base is readily soluble in diluted caustic soda solution or hot water,

moderately soluble in alcohol, sparingly or I not at all soluble in dilute soda solution,'ether and acetone. It crystallizes from alcohol or Water in little, hard, regularly formed crysmelting point of 216 C. to 217 C. It is diflicultly soluble in alcohol and acetone and readily soluble in water. The free base crystallizes from water in small laminae; it is readily soluble in diluted alkalies'and in hot water and very'sparingly soluble 1n ether, It melts at 143 C. to144 C. while swelling in an analogous manner the 7 -hydroxynaphthalene-l-biguanidine or the 7 -hydroxynaphthalene-2-biguanidine may be obtained.

' The following examples serve to illustrate ourvinvention, but they are not intended to.

The hydrochloride of the 7 hydroxynaphthalene-l-biguanidine crystallizes from water in form of laminae and meltsat 235 C.

to 237 (3., while becoming brown and swelling up. The hydrochloride of 7 -hydroxynaphthalene-2-biguanidine melts at 218 C. to 219 C.

be used for the subsequent developing of Y papers which only carry the diazo component.

Such substances may also be added to the solutions of the guanidines as are capable of making the diazo compounds more stable or more readily soluble, such as, for instance,

naphthalene trisulfo'nic acid or metallic salts orsuch as serve for improving the ground or for forming lacquers of the dyestuffs which are produced.

We claim:

1. Process of preparing azo dyestufi components, which consists in causing a cyanamide to act upon a compound of the following constitution:

wherein R stands for the naphthalene nucleus non-substituted in orthoor para-position to the hydroxy group. 2. Process of preparing azo dyestufl' components, which consists in causing dicyandiamide to act upon a compound of the fol lowing constitution:

wherein R stands for the naphthalene nucleus non-substituted in orthoor para-position to the hydroxy group.

' 3. Process of preparing azo dyestufl components, which consists in causing dicyandiamide to act upon a compound of the 01.-

lowing constitution:

wherein one of the Xs stands for NH,, the

other Xs for hydrogen atoms and one of the Ys for OH and the other Ys for hydrogen atoms.

4. Process of preparing azo dyestufi components, which consists in causing dicyan- I Z for the residue diamide to act upon a compound of the following constitution:

wherein one X stands for H, the other X for N11 and one Y for H and the other Y for OH.

5. Process of preparing azo dyestufi components, which consists in causing dicyandiamide to act upon 1.7-aminonaphthol.

6. As new products, compounds of the following formula:

NHX oizr wherein R stands for a naphthalene nucleus non-substituted in orthoor para-position to the hydroxy group and X for a residue of the group consisting of I --CNH; or -c-Nn-o- NH,

NH H NH said products being soluble in caustic alka- 4 lies and in acids.

7. Asnew products, compounds of the following formula:

Y t wherein one of the Zs stands for the residue NHX, X being a substituent of the group consisting of --ONH, or -cNH-c-NH,

the other Zs for hydrogen and one of the Ys stands for OH, the other Ys stand for H, said products being soluble in caustic alkalies and in acids.

8. As new products, compounds of the following. formula wherein one Z stands for hydrogen, the other NHX, X being a substituent of the group consisting of I ;Q NH| or -o-NH-o-Nm H tin and one Y stands for hydrogen, the other Y for OH, said products being soluble in caustic alkalies and in acids.

9. As new products, compoundsof the following formula: e

. "NH-x yielding a, hydrochloride which crystallized from water forms laminae melting at 235 C.-237 (1., while swelling up and turning a brownish color.

In testimony whereof, we afiixour signatures.

EDUARD SPRONGERTSQ MAXIMILIAN PAUL SCHMIDT. ROBERT FRANKE. 

